RU2094443C1 - Polymeric compositions, stable aqueous polymeric dispersion, method of preparation thereof, dried powder, film-forming composition for treatment of paper, method of application of film coating onto paper, and paper material - Google Patents

Abstract

FIELD: chemistry of polymers. SUBSTANCE: polymeric composition in film form comprises water insoluble polymer based on vinyl and diene monomers having vitrification temperature of lower than 55 C, in which at least 50 % particles have size of less than one micron, and water soluble component which is water soluble polymer capable of inhibiting water insoluble polymer particles from being adhered to each other, or mixture of water soluble polymer with compound having identical properties. Particles constitute 5-10 % by weight of water soluble polymer. Water insoluble polymer to water soluble component weight ratio is from 3-75 to 25-97. Water insoluble polymer is copolymer obtained from monomers of group consisting of ethylene, vinyl acetate, 1,3-butadiene and styrene, and water insoluble polymer is butadiene copolymer. Polymeric composition may be in the form of fried powder or dry film. Polymeric composition in the form of dry film is prepared by mixing above-mentioned components to form dispersion, and dispersion is then applied onto solid surface and dried. Stable aqueous film-forming dispersion is prepared of water-insoluble polymer to water soluble component weight ratio of from 20-60 to 40-80. Film forming polymeric composition is used as coating on paper, for which purpose composition in the form of dispersion is applied onto paper material at room temperature and thereafter dried in drier. EFFECT: improved properties of polymeric compositions. 64 cl, 16 dwg , 16 tbl

Description

 The invention relates to hardened films of water-soluble polymers and stable polymer dispersions that can be dried to obtain such films. More specifically, the invention relates to dried films of water-soluble polymers, hardened by non-adherent particles of a water-insoluble polymer, wherein the film contains a water-soluble component and a water-insoluble component.

 Starch is a water-soluble film-forming polymer, but starch films are not widely used because they are brittle, usually of low strength, do not give significant gloss to paper coatings and are often not compatible when mixed with other polymers. Although the best starch films are known to be obtained from starch polymers having a high molecular weight and high concentrations of straight chain polymers, such aqueous solutions of starch have undesirably high viscosities (it is known that starch is a water-soluble polymer). Thus, in order to obtain strong starch films, very dilute starch solutions are used, requiring the removal of very large quantities of water through expensive drying operations.

 One way to reduce viscosity and increase the solids content before film formation is to liquefy starch by hydrolysis of polymer starch chains. Unfortunately, such a dilution reduces the strength and elasticity of the resulting film. As the starch films dry, the hydrogen of the polymer chains binds to each other, which leads to significant shrinkage. Shrinkage leads to the formation of stresses in the final film, which can destroy, form cracks, deform the film. In addition, hydrogen bonds between starch molecules cause a phenomenon known as retrograde or regression. In this case, the chains can bind so tightly that they will not be redispersed even in boiling water. Other hydrocarbon and non-hydrocarbon film-forming water-soluble polymers suffer from most of these disadvantages. Various attempts have been made in this field to improve the properties of starch and other water-soluble films, but most of them have brought only minor quality improvements. One of the improvements of interest is the increase in the fractions of the linear chains of the polymer, which is amylose. Although this gives films with increased strength, their use is limited by their high cost, the difficulty of dispersing the original high molecular weight amylose starch granules and the increased ease of regression of linear molecules. To be useful, plasticizers or humectants must be added to these films. Again, other hydrocarbon, as well as non-hydrocarbon, water-soluble film-forming polymers experience similar difficulties.

 For a long time used a mixture of starch or other water-soluble polymers and latexes as film-forming compositions. In these cases, however, the resulting films contain portions of adherent particles of a water-insoluble latex polymer dispersed between the numerous domains present in the hydrophilic water-soluble polymer. It must be assumed that the formation of a film from latex by adhesion involves the first operation of the loss of water, followed by direct interaction of the polymer particles or the mixing of polymer chains, leading to the loss of the discrete structure of the particles.

 These films of a mixture of a water-soluble polymer and latex, apparently, consist mainly of a continuous adhering latex phase, alternating with areas or domains saturated with a water-soluble polymer. No attempt has been made to protect the latex from sticking together. In fact, there have been attempts to facilitate the adhesion of particles of a water-soluble polymer, since it was believed that such coalescence is necessary for the formation of a continuous film having the desired properties, including strength.

 The area in which such materials have found application is the coating of paper. When starch is used to coat paper, it is often mixed with latex to form a binder system, which, when mixed with pigment, forms the base color of the coating. Unfortunately, films with adherent polymer particles used as a binder in paper coating compositions tend to shrink. They also have significantly reduced dispersibility in water compared to water-soluble polymers. In addition, when latex particles stick together to form a film, subsequent shrinkage can cause defects such as blotches that can be harmful to gloss. Coatings containing one starch as a coating are weak and tend to wrinkle, resulting in a rough surface having a low gloss. Thus, there is a need in the art for aqueous dispersions with improved film-forming properties that can be used as binders in color coating compositions and other end use applications.

The present invention relates to hardened films, including films rapidly dispersible in water, and stable polymer dispersions that can be dried to produce such films. In particular, the invention relates to films containing a water-insoluble component and a water-soluble component, hardened by particles of a water-insoluble polymer, which, by their nature, are capable of sticking, are generally not sticky. Such films can be easily redispersed in water, if necessary. The significant lack of adhesion of particles capable of sticking, insoluble in water, makes the films easily redispersible, without making separate assumptions for crosslinking or lowering the solubility. Thus, the invention provides stable aqueous dispersions capable of producing such hardened films. Stable polymer dispersions may contain mixtures of water-insoluble and water-soluble components or the product of the polymerization reaction of one or more unsaturated monomers carried out in the presence of water-soluble components. Such reaction products include grafted copolymers, including graft polymers of starch. Aqueous dispersions are characterized by the ability to form, when subjected to drying in an atmosphere of air at about 70 ^° F, a film hardened by non-adherent particles of a water-insoluble polymer. Since it is possible for particles of water-insoluble polymer to stick together at other temperatures and conditions, since the dispersions according to the invention can all form films, hardened by non-stickable, sticky particles, dried at 70 ^° F.

 Aqueous polymer dispersions and films obtained according to the invention are characterized by unique properties that are valuable when applied in the field of coatings in general and paper coatings in particular. In particular, films obtained using the dispersions of the invention are characterized by high levels of strength and toughness. If dispersions are used as a binder in color coating compositions, a high level of printing gloss is obtained. The films contain a continuous phase of a water-soluble polymer, hardened by non-coalesced particles of submicron size, which provide toughness and mechanical strength of the film. Non-adherent particles also absorb shrink stress and thereby contribute to a smooth, continuous film surface.

 In cases where films are readily dispersible in water, the invention provides dried powders capable of conveniently dispersing, again in water to form stable aqueous dispersions, and methods for preparing and dispersing these powders. In addition, the invention provides coating color compositions containing aqueous dispersions according to the invention, including coating compositions containing more than 60% solids by weight, together with methods for coating substrates, including paper and other substrates coated with them.

 Dry stable reaction products of the mixture according to the invention provide several advantages. In particular, the products are redispersible when added to water, and will essentially have the same physical properties, including particle sizes after drying and redispersion, as before the initial drying. This leads to a number of commercial advantages, including the ability to receive and store a dry product, which can later be conveniently redispersed later. Dry re-dispersible products reduce the cost of transported materials, such as binders for color coatings, as there is no water. The invention makes it possible to produce a dry product for a long time, during which it could not be stored in the form of a stable liquid dispersion. The invention also allows the dry material to be hydrated again to a higher concentration of solid than the concentration of the solid at which it was originally made. In addition, a dry product can be used directly as a dry material in those applications where the liquid cannot be used. Alternatively, it can be used dry in applications, such as adding directly to an aqueous dispersion containing a coloring pigment for coatings.

 Figure 1 presents a 100% enzyme-diluted starch film; in FIG. 2 enzyme-diluted starch film, including 3 wt. latex; in FIG. 3 photograph of an enzyme-diluted starch film containing 6 wt. latex; figure 4 photograph of an enzyme-diluted starch film with a content of 12 wt. latex; figure 5 photograph of an enzyme-diluted film comprising 24 wt. latex; Fig.6 photograph of an enzyme-diluted starch film comprising 30 wt. latex; 7 is a photograph of a starch film diluted with an enzyme, including 40 wt. latex; in FIG. 8 photograph of an enzyme-diluted starch film comprising 60% latex; Figures 9 and 10 are micrographs showing the dispersion of the reaction product of styrene, butadiene and starch, and the product formed by it; 11 and 12, a dispersion containing a mixture of latex and starch, and the product formed by it; in FIG. 13 electron micrograph obtained by scanning the latex film; on Fig. scanning electron micrograph of a film from a mixture of latex-starch; on Fig scanning electron micrograph of a film obtained from a mixture of latex and diluted with starch enzyme; in FIG. 16 is a scanning electron micrograph of a film obtained from a copolymerization product of styrene, butadiene and starch.

 The invention provides compositions that significantly improve the properties of starch films and other water-soluble film-forming polymers, while avoiding the problems that arise from other attempts to improve these properties. The present invention uses fine particles of a water-insoluble polymer to harden the continuous hydrophilic phase of water-soluble polymers. This hardening by water-insoluble particles sticking together gives beneficial properties to films, such as impact strength, tear resistance and the like. In addition, this hardening is especially important in cases where low molecular weight water-soluble polymers are required to use higher concentrations of solids. In addition, the properties of films of high molecular weight water-soluble polymers can also benefit from this hardening.

 Another unexpected aspect of the invention relates to the ability to maintain non-coalescing submicron size particles of a hydrophobic polymer in a film of a water-soluble polymer after drying. It is well known that an irreversible compound of submicron particles of a water-insoluble polymer during drying is known. After removal of water, the particles usually bind in a substantially irreversible manner, known in the art as adhesion, but sometimes refer to coagulation, aggregation or agglomeration. Used in the description, the term "cohesion" will refer to a substantially irreversible combination of particles, including the deformation and fusion of polymer chains along the boundaries of the particles to form a sequence of a long series. Most unexpectedly, there is no tendency to stick together capable of sticking polymer particles in the scale under rather severe drying conditions at elevated temperatures.

According to the invention, the films contain a rare structure, while they are hardened by the ability to stick together particles of a water-insoluble polymer, which are often elastomeric and which, since they are not sticky and evenly distributed in the film, impart toughness and mechanical strength to the films. Films according to the invention include the following components: (1) small, cohesive particles of a water-insoluble polymer, such as particles obtained by emulsion polymerization; (2) one or more water-soluble polymers; and (3) a component capable of ignoring the adhesion of particles of a water-insoluble polymer if this function is not performed by the water-soluble polymer (s). Dried films according to the invention can be obtained from stable aqueous dispersions according to the invention by applying the dispersion to the surface and drying. Such dispersions contain a water-insoluble component and a water-soluble component, in which (a) the water-insoluble component contains cohesive particles of a polymer having a glass transition temperature (T _g ) below 55 ^° C, and most particles are less than one micron in size; and (b) the water-soluble component comprises a water-soluble polymer, such as starch or starch hydrolyzate, capable of inhibiting the adhesion of polymer particles; or a water-soluble polymer and a component capable of inhibiting particle adhesion, such as, but not limited to, a polyol. Particles capable of sticking water-insoluble polymer in the dispersion contain more than three weight percent solids. The water-soluble component contains more than 25 wt. solids. Water-soluble polymers can be film-forming polymers, such as starch, but they can be non-film-forming polymers, which, however, form a film in the implementation of the present invention. However, if the starch is a water-soluble component, then it is a starch hydrolysis product having an intrinsic viscosity of less than 0.12 dl / g.

The invention further provides a dried powder capable of being easily dispersed in water to form a stable aqueous dispersion containing a water-insoluble component and a water-soluble component, in which more than 3 wt.% Water-insoluble polymer particles are capable of sticking together. solids forming the dispersion, while the water-soluble component is more than 25 wt. solids dispersion. In particular, the water-insoluble component contains cohesive polymer particles having a glass transition temperature below 55 ^° C, and most of the particles are less than one micron in size. The water soluble component comprises a water soluble polymer capable of inhibiting the fusion of said polymer particles, or a water soluble polymer and a component capable of inhibiting the fusion of polymer particles. The dried, dispersible powder according to the invention can be obtained by preparing stable aqueous dispersions according to the invention and drying the dispersion under conditions selected to avoid sticking together of particles of a water-insoluble polymer. Dispersions can be dried by various means, since there is a slight tendency to particles stick together even at extreme temperatures. Such drying means include spray drying, drum drying and vacuum drying (including freeze drying), with spray drying and freeze drying being preferred. These dispersions can also be treated with a selective precipitation solvent. In addition, dispersible powders can be obtained from the redispersible films of the invention by grinding the film. Dried powders are convenient to transport and can be redispersed in water if an aqueous dispersion is needed.

 Stable aqueous dispersions can be obtained by polymerizing unsaturated monomer compounds in the presence of starch or other water-soluble polymer components to form a reaction product, which is a graft polymer of starch. Alternatively, dispersions can be prepared by simply mixing or mixing a water-insoluble component containing polymer particles capable of sticking with a water-soluble component, including a water-soluble polymer and, optionally, and if necessary, a component capable of inhibiting adhesion. A variety of mixing methods may include (1) adding polymer particles to the aqueous dispersion of the water-soluble component; (2) adding dry water-soluble components to an aqueous dispersion of particles of a water-insoluble polymer; (3) a combination of dry particles of a water-soluble component with dry particles of a water-insoluble polymer and dispersion of the dry components in water; and (4) a combination of an aqueous dispersion of a water-soluble component with an aqueous dispersion of particles of a water-insoluble polymer. Dry mixing methods can advantageously obtain dispersions having a high solids content of up to 60 wt. and more.

 According to an additional method, dry redispersible powders can be obtained by selective solvent precipitation. In particular, an aqueous dispersion, such as a dispersion containing a graft polymer of styrene-1,3-butadiene and starch (Penford Products Co. Cedar Rapids JA) "PENGLOSS" (pengloss) can be slowly added to a solvent, such as isopropanol, precipitated from isopropanol and is subjected to vacuum filtration. The precipitate can then be dried in an oven and ground in a ball mill to obtain a fine powder.

 The invention also provides coating color compositions containing a pigment and a binder comprising a dispersion according to the invention. Colored coatings can also be obtained with a high solids content of up to 60 wt. and more. The dry materials according to the invention can actually be mixed directly with pigment, such as clay in the final stage. Coating dyes can be used to coat paper and other substrates by coating and drying the coating. Paper coated using binders according to the invention exhibit increased printing gloss, hardness, surface brightness and, together with opacity, improved porosity and printability. These improved properties, apparently, are the result achieved according to the invention due to the hardened structure.

 Water soluble component. The water-soluble component comprises a water-soluble polymer capable of inhibiting the adhesion of water-insoluble polymer particles capable of sticking together, or a water-soluble polymer and a component capable of inhibiting the adhesion of polymer particles. The water-soluble component contains from 25 to 97 wt. solids contained in the final composition. The water-soluble component contains at least 25% of the total level of solid particles, since this amount is apparently the minimum required for the formation of a film according to the invention. Preferably, the water soluble component contains from 50 to 80% of the total solids.

 Water-soluble polymers useful for the purposes of the invention are film-forming polymers. Suitable water soluble polymers include carbohydrates such as starch obtained from various plant sources, including varieties of high molecular weight amylose and amylopectin. By "starch" as used herein is also meant water-soluble, film-forming polymeric materials derived from starch, including starch derivatives, such as starch hydrolysis products, modified starches, modified starch derivatives and maltodextrins. Other water-soluble polymers useful for the purposes of the invention are polyvinyl alcohol, cellulose derivatives, natural polysaccharide resins and their derivatives, polyethylene glycol, water-soluble acrylic compounds, water-soluble polyesters, polyvinyl pyrrolidone, casein, gelatin, polymerized polymers, solubilized polymers, polymers styrene and maleic anhydride, polyethyleneamine and any water-soluble polymers. Particularly preferred are starch, its derivatives, modified starches and their derivatives, liquefied hydroxyalkyl starches, polyvinyl alcohol, cellulose derivatives, polysaccharide resins, polyethylene glycol and maltodextrin. Most preferred are modified starch derivatives and hydrolyzed starches.

 One of the advantages provided by the present invention is that depolymerization of a water-soluble polymer can be carried out in order to obtain an advantage in high solids content, low viscosity and reduced shrinkage without compromising the elasticity and strength of the hardened film. A particularly preferred material is the starch hydrolysis product, liquefied so that it has an intrinsic viscosity of less than 0.12 dl / g.

 Components capable of inhibiting adhesion. In many cases, the water-soluble polymer itself or its components will prevent the particles of water-insoluble polymer from sticking together. For example, liquefied starches, including maltodextrins, and in particular starch hydrolysis products having an intrinsic viscosity of less than 0.12 dl / g, can prevent the particles of a water-insoluble polymer from sticking together.

 In other cases, it may be necessary to add additional material to prevent this coalescence of particles of the water-insoluble polymer in the film of the water-soluble polymer. Therefore, a component with a low intermediate molecular weight can be incorporated into a water-soluble component to inhibit such adhesion. Suitable components include water-highly soluble and water-miscible components such as urea, low molecular weight polyvinylpyrrolidone, amino acids and polyols, for example glucose, sucrose, maltose, maltodextrins, glycerin, propanediol, sorbitol, pentaerythritol, cyclodextrose, polydextrose, polydextrose. Components capable of inhibiting adhesion can be mixed dry or in liquid solution with a dry or dispersed water-soluble polymer, or in a mixture of insoluble particles, or in a mixture of particles of a water-insoluble polymer and a water-soluble polymer. Concentrations of 5 and 10 percent or more of the components capable of inhibiting adhesion are usually sufficient to carry out the present invention, but one skilled in the art can easily determine the desired concentration to be added to the component, which determines the type and ratio of the film-forming polymer and the water-insoluble component in any specific mixture.

Water insoluble components. Water-insoluble components contain sticky particles of a water-insoluble polymer and optionally contain non-sticky particles of a water-insoluble polymer. For the purposes of the present invention, a particle of a water-insoluble polymer is considered to be “capable of sticking” if a film formed from such polymer particles dispersed in water requires a temperature not exceeding 85 ^° C. to stick together at atmospheric pressure. Particles are considered to coalesce if a substantially irreversible combination of particles takes place, including deformation and fusion of polymer chains along the boundaries of particles with the formation of long-order sequences. In addition to water-insoluble polymer particles, the water-insoluble components may also optionally contain non-cohesive water-insoluble polymer particles that do not stick together during drying. Such non-sticking polymer particles include materials such as polystyrene particles, and may not necessarily be present in the water-insoluble component of the compositions at concentrations that do not interfere with the hardening effect of the water-insoluble polymer particles being able to stick together.

 Particles of water-insoluble polymer are from 3 to 75 wt. the solids content of the compositions according to the invention with a more preferred content of from 10 to 66 wt. and most preferably from 20 to 50 wt.

 We believe that particles of water-insoluble polymer capable of sticking together harden and impart beneficial properties to the films of the invention by absorbing stresses and strains during and after film formation. Additionally, while maintaining particles of a water-insoluble polymer in a non-adherent state, the shrinkage that usually appears is substantially reduced during the drying process. Further, the formation of relatively large domains of adherent water-insoluble particles in the film is prevented, leading to a more uniform structure and surface of the film. This uniformity leads to more uniform wetting if the surface of the film is wetted with various materials. This is advantageous when the hardened film according to the invention is applied as a coating binder for coating paper for offset lithography and other printing processes. The relatively large variation interval on the surface of the paper leads to differences in wettability when printing with aqueous ink or anhydrous printing inks. Traditional binders contain latex and starch, in which latex particles stick together during the drying process, leading to variations in surface wettability. This phenomenon is known in the field of coating as migration of the binder, resulting in printing defects, known as uneven coloring (mottling).

 For the implementation of the present invention, it is preferable that most of the particles of water-insoluble polymer have a size of less than one micron and it is particularly preferred that at least 90% of the particles have a size of less than 0.5 microns and most preferably at least 90% of the particles have a size less than 0.3 microns. Although smaller particles of a water-insoluble polymer tend to stick together, they also give superior hardened properties compared to the same mass of larger particles.

 The invention, as can be seen, is able to use widely various water-insoluble particles. In particular, particles derived from dienes and other unsaturated (vinyl) monomers are suitable for the purposes of the invention. Such diene monomers include 1,3-butadiene, isoprene, chloroprene, cyclobutadiene and divinylbenzene. Suitable unsaturated monomers include alkyl acrylates, hydroxylated methacrylic acid alkyl esters, alkyl vinyl ketones, substituted acrylamides, methacrylic acid, N-hydroxymethyl acrylamide, 2-hydroxyethyl acrylate, crotonic acid, itaconic acid, fumaric acid, vinyl malic acid, malic acid, malic acid, malic acid, malic acid, , vinylcarbazole, N-vinylpyrrolidone, vinylpyridine, chlorostyrene, alkylstyrene, ethylene, propylene, isobutylene, vinyltriethoxysilane, vinyl diethylmethylsilane, vinyl tildihlorsilan, trifenilvinilsilan, 1-vinyl-1-trimethylsilyl-14-crown-5. Preferred monomers include methacrylic acid methyl ester, vinyl acetate, acrylonitrile, silicon monovinyl compounds, including vinyl trimethylsilane, ethyl vinyl ether, chlorostyrene, vinyl pyridine, butyl vinyl ether, 2-ethylhexyl acrylic acid, isoprene, chloroprene, butyl vinyl vinyl ether and styrene is most preferred. Of the polymer particles obtained by polymerization of the monomers of the above group, particles obtained from ethylene and vinyl acetate and 1,3-butadiene and styrene are particularly preferred. Styrene-butadiene lattices are particularly preferred and include pure styrene-butadiene lattices, as well as copolymers of styrene and butadiene with other monomers.

 These water-insoluble polymer particles can be prepared independently and mixed later in the wet or dry state with a water-soluble component, or they can be prepared by reacting in the presence of water-soluble polymers, as described in U.S. Patent No. 5,003,022, which is described in the bibliography. This patent discloses grafted copolymers which are reaction products of liquefied gelled starch with one or more vinyl grafted monomers, wherein the grafted vinyl monomers contain at least 10 wt. diene. We believe that polymerization reactions carried out in the presence of starch or another water-soluble polymer according to the invention can lead to the grafting of unsaturated monomers to water-soluble polymer molecules such as starch. Therefore, the "reaction product" used in the description should be understood as including graft copolymers of starch, if referring to the products initiated by the proxides and persulfates of the reactions described below.

Agents for chain transfer to monomer. Where the dispersion contains a “reaction product”, conventional chain transfer agents known in the manufacture of synthetic rubbers as “modifiers” can be used to control the molecular weight of the formed polymer. Suitable chain transmitters include materials such as n-dodecyl mercaptan, n-cetyl mercaptan, bromoform, carbon tetrachloride and the like in an amount ranging from 0.01 to 0.5% by weight of monomers, preferably from 0.1 to 1.0%
Initiators. Initiators (catalysts) suitable for the purposes of the present invention include those materials that initiate free radical polymerization in the presence of starches and other water-soluble polymers to produce aqueous dispersions according to the invention. Initiating polymerization on water-soluble polymers can lead to vaccination. Suitable initiators include organic and inorganic peroxides, azo compounds and persulfate compounds. Preferred free radical initiators are hydrogen peroxide and persulfate ions, and potassium persulfate is particularly preferred for use with the derivatives and / or liquefied starches of the invention. Persulfates can be in amounts of at least about 0.01% by weight of the monomers used, but are preferably used in the range of 1.0 to 10%. Persulfates can be used in solid form. This application allows to obtain dispersions with a high solids content. The persulfate initiator can be used alone or in a mixture with other initiators. In addition, the initiator may be added immediately or during the polymerization.

 In some cases, reducing agents are sometimes required to activate the decomposition of the above-mentioned free radical polymerization initiators. Suitable reducing agents may include ammonium iron (2) sulfate, ascorbic acid, sodium bisulfate, sodium metabisulfite and sodium thiosulfate. These reducing agents can be added immediately at the beginning or during the reaction.

 Surfactants. Surfactants can be used to stabilize aqueous dispersions and can be added either before the reaction or at the end of the reaction. Suitable types of surfactants include cationic, anionic, amphoteric and nonionic surfactants. Care must be taken to select a surfactant so that it does not interfere with the reaction or, when using the final dispersion in the coating process, does not cause clay flocculation or undesirable viscosity in the dispersion. Surfactants can usually be used in amounts of up to 10% by weight of monomers, preferably from 0 to 5.0%, using sodium dodecylbenzenesulfonate.

Reaction conditions In the case where the polymer dispersions according to the invention are products of an initiated free radical polymerization reaction carried out in the presence of a water-soluble polymer, this polymer is preferably a liquefied starch derivative. The starches used according to this aspect of the invention are cooked gelled to a solids content of 20 to 40% (dry basis), preferably 30 to 40%. The cooked gelled liquefied starch paste is then placed in a reaction vessel capable of supporting and withstanding the pressure of the reaction medium. Regardless of whether starch or other water-soluble polymers are used, various monomers can interact to form polymer dispersions according to the invention. A preferred combination of monomers is styrene and 1,3-butadiene. Due to the relatively high volatility of 1,3-butadiene, it (and other gaseous monomers) interacts under pressure. In general, the more 1,3-butadiene is present in the reaction mixture, the higher the pressure at which the reaction proceeds. The maximum pressure during the reaction is usually from 2.0 to 20 kg / cm ² (or more).

One or more surfactants may be added at any time during the reaction process. If a surfactant is added, then preferred amounts are in the range of 10% of the total weight of the monomers, and particularly preferably in amounts in the range of 1 to 5
A free radical polymerization initiator or initiators may be added at any time during the reaction process.

 A preferred method of using free radical polymerization initiators involves adding from 1 to 5% (of the total weight of monomers) to the water-soluble polymer before adding monomers, with 5% (of the total weight of monomers) being added incrementally during the reaction.

 The weight ratio of the total unsaturated monomer to the water-soluble polymer is preferably in the range from 2:10 to 30:10 and the ratios from 6:10 to 8:10 are most preferred. 1,3-butadiene can interact with water-soluble polymers in the presence of other monomers. If 1,3-butadiene and styrene are used as unsaturated monomers, the amount of 1,3-butadiene is preferably in the range of at least 10% and preferably up to 70 wt. from monomers. Most preferably, when 1,3-butadiene is present in weight concentrations of 20 to 40% in combination with styrene in concentrations of 60 to 80%, the Monomer or monomers may be added at the beginning or during the polymerization reaction depending on the reaction conditions. Monomers are preferably added after the addition of a surfactant and a free radical polymerization initiator. It is preferable to add less volatile reagents at the beginning and more volatile reagents are added later.

The reaction of the water-soluble polymer and the unsaturated monomer can be carried out in a wide temperature range depending on the type of monomers and the catalysts used. Normally, the temperatures are in the range of 25 to 120 ^° C., and preferably in the range of 50 to 90 ^° C. The reaction mixture is preferably stirred since it is heated.

 The reaction time ranges from 0.5 to 24 hours after the addition of the catalyst and is usually sufficient to obtain a final dispersion with suitable properties. In particular, a reaction time of 2 to 12 hours has been found to be particularly preferred for the preparation of a suitable product.

It is desirable that the level of residual monomers be minimized in the final reaction product. Therefore, processing may be required upon completion of the reaction. Preferred treatments include administering an additional initiator. It was found that vacuum distillation with steam reduces the concentration of residual styrene, giving a product with a lower viscosity and high solids content. Another method involves carrying out the reaction at 70 ^° C. for 3 hours and then at 90 ^° C. for 2 hours with vacuum steam distillation, while another method involves using a jet autoclave to effectively remove residual monomer.

 The products according to the invention in the form of back-dispersible dry powders can be advantageously used as binders in paper coating technology. Topcoat color compositions typically contain pigments, such as clay, together with binders and various special additives, such as crosslinking agents and lubricants. Liquid coating dyes are then applied to paper substrates using methods well known in the art and shown in several examples below.

 The binder portion of the coating dye contains a mixture of latex and starch, with latex usually used as an emulsion with a content of approximately 50% solids. Since it is usually desirable to use a binder with higher solids content, such binders are not widely used. The starch used in coatings is usually gelled or cooked in water with about 30% solids content or less. Pigments can be added dry or in the form of suspensions with approximately 70% solids content. Thus, when preparing a color coating, the total solids content can be limited by the water content introduced with each of the coating components, and it can be very difficult or costly to maximize the solids content, which can be done on special coating equipment.

 The dry, redispersible powder according to the present invention makes it possible to eliminate water that normally accompanies latex and starch present in the color coating, while greatly simplifying the preparation of coating dyes having a very high solids content. Not only less water must be removed during the drying process, but also a lower water content leads to a decrease in large shrinkage of the coating on paper during drying. The dry redispersible powder according to the invention can again be dispersed in water with a solids content significantly higher than in the original dispersion, and used as such to obtain a coating having a high solids content, i.e. 60% solids or higher. Alternatively, the powder may be added by mixing directly into an aqueous dye suspension to disperse the powder in the presence of a pigment. Even if dyes with a high solids content are undesirable, the powder can be advantageously used to obtain color coatings in any range of solids content, and the color coatings thus obtained do not really differ from coatings obtained using the initial dispersion before drying.

 If the dry powder according to the invention is used in its most preferred form, the coating dye thus created is indeed indistinguishable from the coating dye obtained using the initial dispersion before drying, as determined by testing the properties of paper coated in a similar manner using both dyes.

 The present invention relates to a film having a substantially smooth substantially flat continuous surface. Although the film may have significant fracture, it is recognized with the naked eye as a planar film, and not as a powder coating or particle coating. A water-soluble polymer film is a film in which the continuous phase contains mainly a water-soluble polymer.

For the purposes of the present invention, a particle of a water-insoluble polymer is considered to be “capable of sticking” if a film cast from such polymer particles dispersed in water requires a temperature of not higher than 85 ^° C. to stick at atmospheric pressure. Particles are considered to adhere if there is a significantly reversible combination of particles involved in the deformation and fusion of polymer chains along the particle boundaries to create a series of long sequences. If the aqueous dispersion contains a mixture of water-insoluble and water-insoluble components, then the ability to stick together particles of a water-insoluble polymer can be determined by testing a film of a water-insoluble component in the absence of water-soluble components, which may contain components that inhibit adhesion.

 Where the aqueous dispersion contains a reaction product, such as a graft copolymer, water-soluble and water-insoluble components, it may not be possible to separate all those water-soluble components that inhibit adhesion from the particles of the water-insoluble polymer. Therefore, the ability to stick together water-insoluble polymer particles of the reaction product is determined by assessing the sticking ability of the polymer particles, which would be obtained during the polymerization reaction in the absence of water-soluble components.

 For example, if particles of a water-insoluble polymer are obtained by the graft polymerization reaction of styrene, butadiene and starch, then the particles are considered capable of sticking if the product of the equivalent polymerization reaction of styrene and butadiene is capable of sticking.

 For the purposes of the present invention, a material is considered fully redispersible if it has substantially the same physical properties after it has been dried and redispersed without heating or vigorously stirring as shown by the aqueous suspension before drying. A material is considered completely redispersed if it meets the following test. According to this test, the dried film or powder is placed on a glass slide and examined under a binocular microscope with a magnification limit of 10-70 times. A drop of distilled water at room temperature is placed on a glass slide or the powder is observed for 10 minutes. The ability of the dried material to disperse in a drop of water is then evaluated. If the material in contact with the droplet forms a white dispersion of particles, similar in appearance to latex without the use of heat, mixing or sensing, then the material is considered to be completely redispersible according to the invention. In addition, a material is considered to be completely or easily redispersible if it is covered with a white “smoke” upon contact with water, and both water-soluble and water-insoluble components migrate quickly to a drop of water at the beginning of a 10-minute test without application heat, stirring or sensing. Thus, redispersible materials are a special subspecies of fully redispersible materials, in which the phenomenon of reverse dispersion manifests itself particularly quickly. To meet the requirements of these tests, there is no need for the film or powder in contact with a drop of water to be dispersed in a single drop of water. However, if the film only whitens or breaks into pieces or requires stirring to disperse and does not form a “haze” or white dispersion, it is not qualified as completely or easily dispersible.

 Based on the above definitions of reverse dispersibility, it was found that a number of starch and unsaturated monomer reaction products, including the commercially available grafted Pengloss starch copolymer (PENGLOSS, Penford Products Co, Cedar Rapids, JA) in a mixture of polymer particles of commercial latex and hydrocarbons usually show the ability to dry to obtain a film or powder and completely and easily redispersible again. The ability of the film to be redispersible depends on the type of water-soluble polymer used, the size of the polymer molecule, the nature and amount of substituents on the polymer, the type of particles, water-insoluble polymer that is combined, or the amount and type of monomer (s) with which it interacts, and the method used to dry the material. According to one aspect of the invention, certain substituted and / or liquefied water-soluble polymers exhibit the ability to stabilize latex dispersion. In addition, it was found that water-soluble polymers allow drying and reverse dispersion of the reaction products of starch and vinyl monomer or mixtures of commercial latexes and substituted and / or liquefied carbohydrates so that the materials have essentially the same physical properties, including particle size, after how they will be dried and redispersed, what they had before drying, to form a film or powder.

 The completely redispersible films and powders according to the invention are mixtures of latex and carbohydrate or the reaction products of starch and an unsaturated monomer, which are used as binders in dye compositions for coating paper. Papers coated with dyes containing binders obtained from redispersible materials have essentially the same properties as determined by gloss and dry mechanical strength as papers coated with dyes containing binders obtained from the same materials before drying. and reverse dispersion.

 Examples. Example 1 describes water-soluble films hardened by increasing amounts of cohesive, water-insoluble particles. Example 2 describes electron micrographs in transmitted light of dispersions according to the invention before and after drying and back dispersion. Example 3 describes scanning microphotographs of films with substantially non-clumping polymer particles and without them.

Example 1. In this example, mixed at various ratios, a mixture of stickable styrene-butadiene latex with a glass transition temperature of 12 ^° C. (Dow 620, Dow Chemical Co. Midland, MJ) and liquefied glass oxidized by the hydroxyethyl ether starch enzyme, a product having elasticity 10 (enzyme-diluted pencot, Pencote, Penford Products Co. Cedar Rapids, JA.), and dried to obtain hardened films. Styrene-butadiene lattices in these films were non-sticky and served to strengthen the films and reduce cracking stresses.

 1 a, a film containing 100% liquefied starch and not containing latex had a significant number of cracks and microcracks. 1b, a film containing 3% latex particles appears to have the structure of a film of a water-soluble polymer hardened by the particles capable of sticking together the polymer of the invention. The presence of even 3% elastomeric latex particles gives a better film with absorption and reduction of shrink stress. Although the film contains a number of cracks, however, the nature of the film is such that it provides improved properties for dyes for applying to paper in which it is embedded as a binder.

 In FIG. 1c shows a film containing 6% latex, which has a smoother surface and fewer cracks. On fig.1d, 1e, 1f, 1g and 1h, respectively, films containing 12, 24, 30, 40 and 60% latex are shown, which show a further improvement in the properties of the films obtained by non-sticky particles of latex. When the concentration of latex reaches 30 wt. then the film is almost completely smooth and without cracks. At concentrations of 40 and 60%, the films have no cracks.

Example 2. In this example, electron microscopy was used to study dispersion particles containing the reaction product of styrene-butadiene and starch and a physical mixture of latex with a diluted starch enzyme before and after drying and reverse dispersion. Styrene-butadiene-starch reaction product dispersion films with a 60: 100 ratio of starch to number, with a solids content of 45.6% based on dry matter and a glass transition temperature of 14.5 ^° C. (Pengloss binder, PENGLOSS, Penford Products Co. Cedar Rapids, JA) and a physical mixture of Dow 620 latex and an enzyme-diluted slightly oxidized hydroxyethyl ether starch (Pencote enzyme-diluted pencote) with a latex to starch ratio of 62: 100 and a solids content of 45% based on dry matter, dried at room temperature and back ispergirovali in ion-exchanged water. For electron microscopy, dispersions were prepared by diluting with distilled water to a solids content of 0.5% and a small drop of each sample was layered between two copper sheets, quickly frozen in liquid cryogen and transferred to a vacuum chamber equipped with a refrigeration stage. There, the sample was fractionated, etched, and then coated with an ultrathin conductive platinum and carbon-supporting film. Then the metal film was removed, purified with acid and washed thoroughly with distilled water. The metal-bearing film, which contains the shadows of the dispersion particles, was then removed in transmitted light by an electron microscope (Model H-7000, Hitachi). Fig. 2a shows a transmission electron micrograph of a dispersion of a styrene-butadiene-starch reaction product, i.e., a Pengloss binder at 20,000 times magnification, and Fig. 2b shows a reconstructed Pengloss binder at 20,000x magnification. Fig. 3a shows a transmission electron micrograph of a mixture of Dow latex and enzyme-diluted starch, and Fig. 3b shows a micrograph of the reconstituted product at 10,000 times. She distinctly showed that, after drying and redispersion, the polymer particles of these dispersions are non-sticky and still clearly retain their original sizes and shapes.

 Example 3. In this example, various films were evaluated using a scanning electron microscope to directly determine the adhesion of particles of polymer insoluble in water. If films that are easily and easily dispersible inevitably have non-adherent polymer particles, then there may still be films having non-adherent particles, but the films are not easily dispersed. These are films containing degraded starch or a crosslinked water-soluble polymer.

 Films were obtained from dispersions including: A) a 100% dispersion of styrene and butadiene latex (Dow 620 Latex); B) styrene-butadiene latex (Dow 620 Latex), mixed in a weight ratio of 1: 2 with liquefied simple hydroxyethyl starch ether (Pencote starch); C) styrene-butadiene latex (Dow 620 Latex), mixed by weight with a dilution product of the enzyme starch hydroxyethyl ether (ET Pencote starch), which was significantly more diluted than product B), and a dispersion of the grafted starch copolymer with styrene- butadiene (PENGLOSS binder) containing one part of the initial monomer in 2 parts of starch.

 The dried films were fractionated so that freshly destroyed collapse (kink) could be examined. In cases where the wafer was too plastic, to facilitate destruction, the samples were immersed for a moment in liquid nitrogen and then destroyed. Destroyed debris and a flat piece of waffle were placed on supports using a copper tape. The debris was oriented so that the broken surface looked up to facilitate research. Samples were metallized by sputtering for 3 min with a mixture of gold and palladium in the presence of gaseous argon before being studied under an IEOL ISM-840 scanning electron microscope.

 Let us now turn to figa-4d. The latex particles of the 100% latex film of FIG. 4a fully adhered to the polymer particles of films obtained from a mixture of latex and enzyme-diluted starch in FIG. 4c and the grafted starch copolymer in FIG. 4d. The latex particles of a latex-starch film of FIG. 4b are largely sticky. Adhesive particles do not completely disperse the film. As such, this film is not considered to fall within the scope of the invention.

 In examples 4-9, various mixtures of water-soluble and water-insoluble components were obtained in the form of aqueous dispersions. Films were cast from the resulting dispersions and examined as described below to determine the degree of re-dispersion ability of the dried film. Based on these studies, conclusions were drawn regarding the cohesion of the water-insoluble polymer particles present in these films that were capable of sticking. In particular, where the dried film remained intact and did not succumb to rapid and / or complete reverse dispersion, it was concluded that particles of the water-insoluble polymer stick together in the film. Such conclusions could be deduced because a film in which particles of a water-insoluble polymer coalesced cannot easily and completely disperse back. In cases where the dried film was partially dispersed when a drop of water was applied and the film remained essentially intact, it was concluded that the particles of the water-insoluble polymer partially or mainly coalesced. If the film is quickly or completely dispersed when a drop of distilled water is applied, it was concluded that the particles of the water-insoluble polymer did not stick together.

 Example 4. Mixtures were prepared from the following materials: commercially available carboxylated styrene-butadiene latex (Dow CP620 NA), a solution of cooked pencot starch, and a dextrose solution. Mixtures were prepared in weight ratios (based on solid), are presented in table 1 below. A single latex sample is included as a control.

Films of the materials described above were cast onto microscope slides and thoroughly dried at room temperature (about 70 ^° F.) for 18 hours. The AD series dispersions were dried to obtain substantially uniform, crack-free films. The dispersion E was very slowly amenable to drying as a result of the water-forming properties of dextrose, and did not form a film. The dried samples were then examined under a binocular microscope with a 10-70-fold magnification limit as follows. A drop of distilled water at room temperature was applied to the sample and observed for 10 min. The following observations were made regarding the redispersibility of wetted samples and conclusions were made regarding the stickiness of particles of water-insoluble polymer in the samples.

 Example 5. Mixtures were prepared from the following materials: commercially available carboxylated styrene-butadiene latex (Dow CP620 NA, available from Dow Chemical Co.), a solution of cooked pencot starch, a slightly oxidized liquid starch ether (product supplied by Penford Phoduct Co.) an enzyme diluted pencote solution (ET Pencote) (starch supplied by Penford Product Co.). Mixtures were prepared in the ratios (based on solids) presented in Table 3.

 The dispersions described above were cast onto microscope slides and thoroughly dried at room temperature. A PENGLOSS binder film (Penford Phoduct Co., a reaction product of styrene-butadiene with an enzyme-diluted starch obtained by the method of US Pat. No. 5,003,022), designated E, was included for comparison. The dried films were continuous and had no cracks. Then the films were studied under a binocular microscope with a 10-70-fold magnification as follows. A drop of distilled water was applied to each film and monitored for a 10 minute period to determine the dispersibility of the film. The following observations were made.

 Example 6. The mixtures were prepared from the following materials: a commercially available carboxylated styrene-butadiene latex (Dow CP620 NA, supplied by Dow Chemical Co.), a partially hydrolyzed polyvinyl alcohol solution (Airvol 203 Air Products and Chemicals Juc.) And a dextrose solution. Mixtures were prepared in the ratios (based on solids) shown in Table 5 below.

 Dispersions of the materials described above were applied to microscope slides and thoroughly dried at room temperature. The dried films were smooth and continuous. Then the films were examined under a binocular microscope with a magnification range of 10-70 times as follows. A drop of distilled water was applied to the film, and the film was observed for 10 minutes. The following observations were made.

 Example 7. Mixtures were prepared from the following materials: commercially available carboxylated styrene-butadiene latex (Dow CP620 NA, available from Dow Chemical Co.), a solution prepared from guar resin (Jaguar gum HP-8, Rhone Poulenc Juc.), A solution of hydroxypropyl methylcellulose (methocel J12MS, Dow Chemical Co.), a dextrose solution and a pencote (ET Pencote) enzyme-diluted starch solution. Mixtures were prepared in the ratios (based on solid) shown in Table 7 below.

 Dispersions of the materials described above were cast onto microscope slides and thoroughly dried at room temperature to form films. Then the films were examined under a binocular microscope with a magnification limit of 10-70 times as follows. A drop of distilled water was applied to each film and the films were monitored for 10 minutes. The following results were obtained.

 Example 8. Mixtures were prepared from the following materials: commercially available carboxylated styrene-butadiene latex (Dow CP620 NA, obtained from Dow Chemical Co.), a solution of polyethylene glycol 1000 (PEG-1000), and a maltodextrin solution with dextrose equivalent to 10 (Maltrin 100, Irain Processing Co.). Mixtures were prepared in the ratios (based on solids) shown in Table 9 below. A single latex sample is included for control (C).

 Dispersions of the materials described above were cast onto microscope slides and thoroughly dried at room temperature. The dried films were smooth and continuous. The films were then examined under a binocular microscope with magnification limits of 10-70-fold as follows. A drop of distilled water was applied to the film and the film was observed for 10 minutes. The following observations are made.

Example 9. Mixtures were prepared from the following materials: a commercially available styrene-butadiene latex (Dow CP620 NA supplied by Dow Chemical Co.), a latex emulsion of a vinyl acetate-ethylene copolymer with a glass transition temperature of about 5 ^° C (Airflex 500, Air Products and Chemicals Juc .), natural rubber latex with a glass transition temperature not specified, but significantly lower than -20 ^o C (H-1400 Heveatex Corp.) and neoprene latex with a glass transition temperature not specified, but significantly lower than -20 ^o C (Neoprene Latex 654 Du Pont) and pencot starch liquefied by the enzyme. Mixtures were prepared in the ratios (calculated on solid), which are indicated in table 11 below. Samples of all four latexes were included as controls (D, E, F, G).

 Dispersions of the materials described above were cast onto microscope slides and thoroughly dried at room temperature until films were formed. Then they were examined under a binocular microscope with a magnification of 10-70 times as follows. A drop of distilled water was applied to the film, and the film was observed for 10 minutes. The following observations were made showing that the lattices vary in their tendency to stick together and that higher ratios of water-soluble polymers do not necessarily inhibit the sticking of the lattices with very low glass transition temperatures. The glass transition temperature is the primary factor affecting the ability to stick together particles of a water-insoluble polymer. Other factors include molecular weight, degree of crosslinking, and surface nature.

 In Examples 10-16, various monomers were reacted in the presence of liquefied starch to produce aqueous polymer dispersions. These reaction products, including grafted starch copolymers, were then dried to form films and tested for dispersibility.

 Example 10. In this example, the liquid, slightly oxidized oxyethyl ether of pencot starch (Penford Phoduct Co. Cedar Rapiols, IA) was diluted with an enzyme and reacted with butadiene and methyl methacrylate (Example 10A) or with butadiene and acrylonitrile (Example 10B) in 2 liter Parr reactors (Parr Instruments) in the presence of a potassium persulfate initiator to obtain a stable aqueous polymer dispersion, which was then dried and redispersed.

When preparing samples, a starch suspension containing 1200 g of Pencote dry starch was cooked on a laboratory stove for about 30 minutes at a solids content of 34.4%. Cooked starch was then cooled to 88 ^° C and liquefied by adding 360 μl of alpha-amylase (Canalpha, Biocon, Sarasota , FL) and cooked starch paste. The mixture was kept at 88 ^° C and stirred for 1 h 40 min. To this material was added 3 ml of hypochlorite (16% active chlorine) to deactivate the enzyme. According to this process, approximately 1307 g of cooked liquefied pasta was added to 2 liter reactors (Parr Instruments) followed by 13.5 g of potassium persulfate and 173 g of water. To the first 2 liter reactor (Example 10A), 292 g of methyl methacrylate and 158 g of butadiene were added. 223 g of acrylonitrile and 227 g of butadiene were also added to the second reactor (Example 10B). The mixture was stirred and heated to about 70 ^{° C.} and held for 10 hours. The mixture was cooled to room temperature and the pH was adjusted to 5.5 with dry sodium carbonate. The reaction products were filtered through a 63 μm (0.0024 in) sieve.

 Films were formed from both products and allowed to air dry overnight. The materials were redispersed by the following method. About 10 g of dried material was weighed in a 100 ml grinder. A sufficient amount of ion-exchange water was added to each sample, which was passed through a 0.2 μm pore filter to bring the solids content to about 15%. Each sample was stirred without heating for about 30 minutes and monitored for the presence of undissolved material. If all material (or almost all material, i.e., more than 99%) went into dispersion, then the sample was filtered through a sieve with 63 μm (0.0024 in) openings and evaluated for the content of undispersed material.

If the sample had a significant amount of undispersed material (more than one or two percent), then heating of the stirred material was used, raising the temperature to 55-75 ^o C and holding for 15-60 minutes depending on how quickly the sample was dispersed. The sample was then filtered through a 63 μm (0.0024 in) sieve to determine the degree of dispersibility of the material. According to the method described above, the film of Example 10A was dispersed when heated to 60 ^° C. and produced less than one percent of adherent particles. The film of Example 10B was dispersed without heating and left less than one percent of adherent particles. Therefore, since the film of Example 10A was ultimately redispersed by the application of mechanical stirring and heat, it was not considered to be rapidly and completely redispersible in accordance with the test method of Example 4, although it is believed that the film of Example 10B satisfies these requirements. Therefore, it was concluded that the polymer particles of Example 10A capable of sticking together, while those of Example 10B did not stick together.

 Example 11. In this example, an enzyme-diluted starch ether was reacted with styrene, butadiene and 2-ethylhexyl acrylate in a 2 liter Parr reactor in the presence of a calcium persulfate reaction initiator to obtain a reaction product that would be a stable aqueous polymer dispersion.

Specifically, 1277 g of Pencote dry starch was cooked in a laboratory step furnace for about 30 minutes with a solids content of about 38.1%. Cooked starch was then cooled to 88 ^° C and 200 μl of alpha-amylase was liquefied for 1 hour and 10 minutes. To this material was added 3 ml of hypochlorite (active chlorine content 16%) to deactivate the enzyme. 1394 g of liquefied starch paste, 13.8 g of potassium persulfate, 7.2 g of sodium hydrogen carbonate, 14 g of water, 223 g of styrene, 106 g of butadiene and 16 g of 2-ethylhexyl ester of acrylic acid were loaded into a 2-liter Parr reactor. The mixture was stirred, heated to 70 ^° C. and kept at this temperature for 8 hours. The mixture was cooled to room temperature and the pH was adjusted to 7.0. The film was formed from the material of the reaction product and left overnight for drying in air. The dry film was redispersed by the method described in Example 10. The film was dispersed without heating and left less than one percent of adherent particles. The film was considered to be completely dispersible according to the test method of Example 4, and therefore, it was concluded that the polymer particles capable of sticking were not sticky.

 Example 12 In this example, enzyme-treated unmodified corn starch (ET Pencote) was reacted with styrene and butadiene monomers in the presence of a free radical initiator, potassium persulfate, to obtain a stable aqueous polymer dispersion. Then the material was dried to obtain a film and back dispersed.

Specifically, the pH of an unmodified raw suspension of starch containing 1100 g of starch containing 42% solids was adjusted to about 6.5 g with a concentrated solution of calcium hydroxide. The suspension was diluted by adding 280 μl of alpha-amylase. Suspension and water were loaded into a steam-heated starch cooking oven to bring to a final calculated solids content of about 37.0%. The water was heated to 195 ^° F (without stirring) and a suspension of starch and enzyme was added at a rate that allowed good mixing (total add time about 22 minutes). The suspension temperature was maintained at 88 ^° C. for an additional 40 minutes. 5 ml of hypochlorite (16% active chlorine) was added to this material to deactivate the enzyme. Evaporation of water during the cooling and liquefaction of starch resulted in a final measured solids content of about 45.5%. About 1222 g of chilled liquefied paste, 13.8 g of potassium persulfate, 364.5 g of water, 233 g of styrene and 111 g of butadiene were loaded into 2 liter Parr reactor. The mixture was stirred and heated to 69 ^° C. and held for 8 hours. The mixture was cooled to room temperature and the pH was adjusted to 5.5 with sodium carbonate. The reaction product was filtered through a 63 μm (0.0024 inch) sieve.

The film was back dispersed by the method used in Example 10. The dried material required heating to 60 ^° C. for back dispersion in water and had less than one percent of sticking particles. The material was not considered completely redispersible according to the test method of Example 4. Therefore, it was concluded that polymer particles capable of sticking together in this film were sticky.

 Example 13 In this example, liquid potato starch hydroxyethyl ester (Polaris LV, Penford Products Co. Cedar Rapids, IA) was reacted with styrene and butadiene in the presence of potassium persulfate polymerization initiator to obtain a stable aqueous polymer dispersion which was cast into a film, dried and dispersed back.

A starch suspension containing 38.3% solids, including 1100 g of dry matter Polaris LV, was diluted by adding 300 μl of alpha-amylase. The suspension was heated with stirring in a steam-heated laboratory oven to 88 ^° C and held for 1.5 hours. Then, the enzyme was deactivated with 3.0 ml of hypochlorite (16% active chlorine). According to this process, about 1470 g of cooked liquefied pasta was loaded into a 2-liter Parr reactor, sodium carbonate, 15.5 g of water, 236 g of styrene and 92 g of butadiene were added. The mixture was stirred and heated to 69 ^° C. and held at this temperature for 8 hours. The mixture was cooled to room temperature and the pH was adjusted to 7.0. The reaction product was filtered through a 63 μm (0.0025 in) sieve.

 The film was formed and redispersed by the method used in example 10. The film was well dispersed without heating and left less than one percent of adherent particles. Obviously, the film was considered completely dispersible according to the test method of Example 4, and therefore, it was concluded that polymer particles capable of sticking did not stick together.

 Example 14. In this example, the highly liquefied amaizo 839 waxy corn starch (Amaizo 839, American Maize Products Co. Hammond, JN) was reacted with styrene and butadiene in the presence of potassium persulfate polymerization initiator to obtain a stable aqueous polymer dispersion.

Specifically, 752 g of amaizo 839 dry starch was cooked in a step laboratory furnace for 2 hours and 15 minutes with 36.9% dry solids. After cooling, 470 g of the cooked paste was placed in a one-liter Parra reactor together with 4.7 g of potassium persulfate, 2.9 g of sodium bicarbonate, 366 g of water, 76 g of styrene and 33 g of butadiene. The mixture was heated with stirring to 69 ^° C. and held at this temperature for 8 hours. The mixture was cooled and filtered through a 63 μm (0.0024 in) pore sieve. The film was formed from the reaction product and allowed to air dry overnight. The dry film was redispersed by the method used in Example 10. The film was dispersed by heating to 60 ^° C. and produced less than 1% of adherent particles. We believe that the material does not belong to fully dispersible according to the test method of Example 4, and therefore we conclude that polymer particles capable of sticking together have stuck together.

 Example 15. In this Star-Dri 5 example (Star-Dri 5 AE Staley Manufacturing Co. Decatur, IL), maltodextrin with a degree of elasticity of 5 waxy corn starch was reacted with styrene and butadiene in the presence of potassium persulfate polymerization initiator to obtain stable aqueous polymer dispersion.

Specifically, 270 g of dry starter 5 were mixed with 442 g of water, 6.6 g of potassium persulfate, 112 g of styrene and 53 g of butadiene in a one liter Parr reactor. The mixture was heated with stirring to 69 ^° C and held at this temperature for 8 hours. The mixture was cooled and filtered through a sieve with 63 μm (0.0024 in) openings. A film was drawn from the material and allowed to air dry overnight. The dry film was again dispersed according to the method used in example 10. The film was dispersed very well without heating and gave less than 1% of adhered particles. We believe that the film is considered to be completely dispersible according to the test method of Example 4, and therefore we conclude that polymer particles capable of sticking in this film did not stick together.

 Example 16. In this example, the Dow 620 latex (Dow Chemical Co. Midland, MI) was mixed with a number of different types of modified corn starch. Films were formed from the obtained dispersions, dried, redispersed, and used as a binder in the dye compositions for applying onto paper, which were then coated on paper. These coated papers were then compared with papers coated with compositions prepared from the same dispersions prior to drying and back dispersion.

 For this example, five batches of paper were coated. Half of each series consisted of paper coated with a paper dye composition prepared with a binder containing dried and redispersible latex “dow 620” in combination with modified corn starch. The other half of each series consisted of paper coated with dye coating compositions prepared on the same binders after they were dried and redispersed.

 Specifically, Dow 620 latex was mixed with five different modified corn starches in relation to 38.3% of Dow 620 latex based on dry weight and 61.3% modified corn starch based on dry weight. Latex and starch were mixed by slowly adding latex to starch with vigorous stirring. The first series of papers (Examples 13A and 13B in Table 13) was coated with a dye composition for coating paper prepared on a binder consisting of 38.3% Dow 620 latex and 61.7% enzyme-liquefied unmodified corn starch (ET Pearl) calculated on dry weight. ET Pearl starch was obtained using the same method used in Example 12 to produce ET Pearl Corn Starch. The following series of papers (13C and 13D in Table 13) was coated with paper dye prepared on a binder consisting of 38.3% Dow 620 latex and 61.7% Penford gum 290 starch (Penford Products Co. Cedar Rapids , IA) calculated on the dry matter. Penford gum 290 starch was cooked but not liquefied by an enzyme in a laboratory step furnace using the method described in Example 11.

 The next series of papers (13E and 13F in Table 13) was coated with a colorant composition for application onto paper prepared on a binder consisting of 38.3% and 61.7% Star-Dri 5 maltodextr on a dry matter basis. Maltodextrin Star-Dri 5 was first suspended in water at 49% solids based on dry matter. The dow 620 latex was then mixed with this suspension.

 The next series of papers (13G and 13H in Table 13) was coated with a dye composition for coating paper prepared on a binder consisting of 38.3% Dow 620 latex and 61.7% Fro-Dex 22 corn starch (American Maize Products Co. Hammond, IN). Fro-Dex 22 was first suspended in water at 50% solids based on dry matter. The dow 620 latex was then mixed with this suspension.

 The last series of papers (13I and 13J in Table 13) was coated with a dye composition for applying to paper prepared on a binder consisting of cooked Penford Jum 290 starch as described in Example 8, in combination with a suspension of CANTAB corn syrup solids (elasticity 97 % solids content 95% dextrose corn syrup (Penford Products Co. Cedar Rapids, IA) and water relative to 70% Penford Jum 290 and 30% solids corn syrup CANTAB calculated on the dry matter. Then, dow 620 latex was slowly added to this mixture with stirring at a ratio of lat Exa Dow 620 as 38.3% to 61.7% of the mixture of Penford Jum 290 starch and CANTAB corn syrup solids (38.3% of the Dow 620 latex, 43.2% of Penford Jum 290 starch and CANTAB corn syrup solids 18 ,5%).

Dye compositions for applying to paper were prepared by mixing a binder, as described above, with a clay slip with a solids content of 70% and then adjusting the pH to 8.3-8.8. A clay slip was obtained by adding Nucley clay (Engclhard) to tap water containing 0.04% polyacrylate and sodium hydroxide (42% solids) as a dispersant (based on solids of commercial products). After adding the binders described above to the alumina slurry and adjusting the pH with ammonium hydroxide, the colorants were mixed thoroughly. Typical coating composition included:
Composition Parts
Layered Clay N 1 (Nucley) 100
Binder 18
Total solids 59 66
pH 8.3 8.8
Dimensionless non-calendered base paper with a density of 12.7 kg / 306.6 m ² (28 pounds, 3300 ft ² ) was coated with dyes for coating on a stepped tape coating machine. Coating dyes were applied at room temperature and immediately dried in an infrared dryer (CCh Enterprises, St. Louis, MO). The weight control of the coatings was carried out by changing the pressure of the clamping tape. All samples coated with coatings were kept at 50% relative humidity and 23 ^° C before testing.

Coated sheets were calendared with BF Perkuis and Sons Supercalender, Chicopel, mA). Calendering conditions are as follows: roll pressure 180 kg / cm, roll speed 23.7 m / min and roll temperature 150 ^° F. Each sheet was calendared through four density stages.

After coating and calendering, the base paper was tested for gloss and IGT. Glossiness determinations were performed by averaging about ten measurements per sheet for three or four coated and calendared sheets of each type using a 75 ^o Glossgrad II gloss meter (J Glossmeter Pacific Scientific, Silver Spring, Maryland). IGT assays were performed on a Reprotest IGT Printability Fester (Reprotest North America, Cherry Hill, NJ).

 The test results of the coating dye compositions showed significant differences in the properties between fresh and inversely dispersed dow 620 latex mixtures, both with Pearl enzyme liquefied starch and Penford Jum 290 starch. to repeat the properties of fresh binder mixtures. Therefore, it can be concluded that at least a portion of the polymer particles capable of sticking together has stuck together.

 In contrast, Star-Dri 5 maltodextrin mixture and Fro-Dex 22 starch hydrolysis products with Dow 620 latex appear to be completely redispersible and equivalent in properties to dispersions of coating dyes containing fresh and inversely dispersed mixtures. It was concluded that the latex particles capable of sticking together in the dried dispersions remain largely un sticky.

 A mixture of Dow 620 latex, CANTAB corn syrup, and Penford Jum 290 starch showed a significant increase in viscosity upon drying and back dispersion, indicating that the polymer particles capable of sticking did not remain significantly unadhesive.

 Example 17. In this example, a PENGLOSS binder sample (Penford Products Co. Cedar Rapids, JA) was freeze-dried, redispersed and used as a binder in a paper dye.

 A PENGLOSS sample was first diluted with ion-exchanged water to a solids content of 20% and then freeze dried in a Lyph-Lock 6 apparatus (Labconco Corporation, Kansas City, Missouri). The freeze-dried product was redispersed in ion-exchanged water at a solids content of 50%. The redispersed material was used as a binder in a coating dye for applying to paper according to the method described in example 16. The results are shown in table 14 below.

Example 18. In this example, the reaction product of styrene, butadiene and starch (PENGLOSS binder) obtained in a laboratory setting was spray dried in a laboratory spray. More specifically, the PENGLOSS binder was prepared from Pencote starch-liquefied enzyme by reacting with the dry solids of styrene and butadiene in a weight ratio of 100 parts by weight. starch ET Penkote, 42 parts by weight styrene and 20 parts by weight butadiene. The reaction was initiated with 1.8% potassium persulfate calculated on the dry matter of starch. The reaction mixture was heated to 162 ^° F and held at 160 ^° F for a total of 8 hours. The resulting PENGLOSS binder had a solids content of 50.4%
The PENGLOSS binder was spray dried in a Niro spray drying laboratory apparatus (Niro, Nichols Ingineering Research Corp.). Inlet air was burned directly by burning gas. The inlet temperature was maintained at 356 ^° F and the flow of PENGLOSS binder began at a rate of 19 l / h. The outlet temperature was 221 ^° F. Samples were taken after equilibrium was established in the system. Prior to testing, the material was passed through a standard 45 mesh sieve to obtain data on reverse dispersibility and coating properties. Data on coatings was obtained by the methods used in examples 16 and 19. The results are summarized in table 15. These results show that the spray dried and back dispersed PENGLOSS binder provides compositions for applying to paper having substantially the same physical properties as the dried and non-dispersed back material.

 Example 19. In this example, paper dye compositions were prepared containing a PENGLOSS liquid binder, spray dried PENGLOSS binder according to Example 18, and a liquid reconstituted PENGLOSS spray dried binder, which contains the spray dried binder material of Example 18, reconstituted in water. Each of the binders was added to two systems with solids 70 and 76%, respectively, and lubricants were added to some coating colorant compositions.

 Alumina slip of nuclei (Nucleu, Engelhard) and hydrosperses (Hydrasperse, JM Hubel Corp.) were prepared with a solids content of 70% by adding clay to tap water containing 0.04-0.05% dispersant from a mixture of polyacrylate and hydroxide (based on available in the sale of materials) based on clay. Calcium carbonate, Carbital 90 (Carbital 90, E.C. C. America America) with a solids content of 76% was used as obtained in the form of a slip.

 Coating dyes were prepared with and without lubricant. Compositions of coating dyes with Nopcote C-104 (Nopcote-104, Henkel Corp.) used as a lubricant resulted in a pH of 8.3-8.6 with ammonium hydroxide prior to the addition of the lubricant. Compositions of coating dyes with Berch 4113 (Berchem 4113, Berchem Inc.) used as a lubricant resulted in a pH of 8.3-8.8 with ammonium hydroxide after the lubricant was added. All coating dyes were thoroughly mixed.

Non-formatted, non-calendered base paper 12.7 kg / 306 m ² (28 pounds per 3300 ft ² ) was dyed, calendared and tested on equipment and under the conditions described in example 16. The results are presented in table 16 below. A comparison of series 16A and 16B shows that the dried and back-dispersed PENGLOSS binder gives a coating dye having substantially the same viscosity as a binder that has never been dried. Series 16D and 16E show the usefulness of a binder for coating paper with a high solids content of about 70%, whether it is added in the form of a vein dispersion (16D) or as dry solids (16E). Series 16F and 16G show the usefulness of a binder in the production of coating dyes with extremely high solids levels of about 74%
Example 20. In this example, a film of a mixture of polyvinyl acetate-polyvinyl alcohol was obtained by the method of Columbus et al described in example 1, US patent N 3442845. The process according to this example was repeated using 62.86 g of latex polyvinyl acetate (55% solids, 5000 centipoise , nonionic, average particle size 3 μm, product Unocal 6206, Unocal Corp.), 14.06 g of polyvinyl alcohol (87-89% hydrolysis, average molecular weight and 23-27 centipoise viscosity (4% aqueous solution at 20 ^o C), (Airvol 523, Air Products and Chemicals Inc.), 4.48 g of glycerin (JF Backer Chemical Co.), 0.12 g of canned food nta (orthophenylphenol, Aldrich Chemical Co.), 0.66 g of a foam dampener (Colloid 581, Rhone Poulenc) and 117.22 g of water.

 The product mixture was filtered through a 100 mesh sieve and stretched into a film on a Mylar Film. The film was carefully dried for three days at room temperature. When the film was examined on a microscope slide in Example 4, the film was very slowly dispersed (4-5 minutes) and then peeled off, slowly thickening and thickening as the polyvinyl alcohol dissolved. Therefore, the film is not considered to be completely back dispersible, and it was concluded that polymer particles capable of adhesion were at least partially adhered.

 Specialists in this field, it should be expected, may appear a number of modifications and variations of the present invention. Only the restrictions imposed by the following claims are legitimate.

Claims (63)

1. The polymer composition in the form of a film, comprising a water-insoluble polymer based on vinyl and diene monomers having a glass transition temperature below 55 ^o C, and a water-soluble component, characterized in that the water-insoluble polymer is a particle of which at least 90% have a size particles less than 1 μm, as a water-soluble component, the composition contains either a water-soluble polymer capable of inhibiting the adhesion of particles of a water-insoluble polymer, or a mixture of a water-soluble polymer with a substance having According to the indicated property, which is contained in an amount of 5-10% by weight of the water-soluble polymer, the mass ratio of the water-insoluble polymer to the water-soluble component is (3 - 75) (25 97).  2. The composition according to p. 1, characterized in that as a water-insoluble polymer contains a copolymer obtained from monomers selected from the group: ethylene, vinyl acetate, 1,3-butadiene and styrene.  3. The composition according to p. 1, characterized in that as a water-insoluble polymer contains a styrene-butadiene copolymer.  4. The composition according to p. 1, characterized in that it contains a mixture of components obtained by mixing a water-insoluble component with a water-soluble component and drying the mixture.  5. The composition according to paragraphs. 1 3 or 4, characterized in that the composition contains at least 90% capable of sticking particles of a water-insoluble polymer with a particle size of less than 0.5 microns.  6. The composition according to paragraphs. 1 3 or 4, characterized in that it contains a water-insoluble polymer in which at least 90% of the particles have a size of less than 0.3 microns.  7. The composition according to PP. 1 3 or 4, characterized in that it contains capable of sticking polymer particles obtained from one or more monomers selected from the group: styrene, 1,3-butadiene, vinyl acetate, ethylene, ethyl vinyl ether.  8. The composition according to PP. 1 to 3 or 4, characterized in that the water-soluble polymer is selected from the group consisting of starch, liquefied starch hydroxyethyl ether, polyvinyl alcohol, hydroxypropyl methyl cellulose, polysaccharide resins, polyethylene glycol and maltodextrin.  9. The composition according to PP. 1 3 or 4, characterized in that it contains a water-soluble component, including a starch hydrolysis product with an intrinsic viscosity of less than 0.12 dl / g.  10. The composition according to p. 1 or 4, characterized in that it contains as a water-insoluble component styrene-butadiene rubber.  11. The composition according to p. 10, characterized in that as a water-soluble component contains a simple hydroxyethyl ether liquefied starch.  12. The composition according to p. 10, characterized in that as a water-soluble component it contains polyvinyl alcohol.  13. The composition according to PP. 1-3 or 4, characterized in that it contains a mixture of components that is readily dispersible in water.  14. The composition according to paragraphs. 1 3 or 4, characterized in that as a water-soluble component, it contains a water-soluble polymer capable of inhibiting the adhesion of polymer particles.  15. The composition according to p. 14, characterized in that it is a film that is completely dispersible in water. 16. A stable aqueous film-forming dispersion containing a water-insoluble polymer based on vinyl and diene monomers having a glass transition temperature below 55 ^o C, a water-soluble component and water, characterized in that it contains at least 90% of particles of a water-insoluble polymer smaller than 1 μm, and as a water-soluble component, it contains either a water-soluble polymer capable of inhibiting the cohesion of particles of a water-insoluble polymer, or a mixture of a water-soluble polymer with a substance having the specified Twomey contained in an amount of 5 to 10% by weight of water-soluble polymer, wherein the weight ratio of water-insoluble water-soluble polymer component is (3 75) (25 - 97), and a total solids content of the slurry is 20 to 60 wt.  17. The dispersion according to claim 16, characterized in that, as a water-insoluble component, it contains a copolymer obtained from monomers selected from the group: ethylene, vinyl acetate, 1,3-butadiene and styrene.  18. The dispersion according to claim 16, characterized in that it contains a styrene-butadiene copolymer as a water-insoluble polymer.  19. The dispersion according to p. 16, characterized in that it contains a mixture of components obtained by mixing a water-insoluble polymer with a water-soluble component.  20. Dispersion according to claims 16 to 19, characterized in that the composition contains a water-insoluble polymer in which at least 90% of the capable of sticking particles have a size of less than 0.5 microns.  21. Dispersion according to claims 16 to 19, characterized in that it contains a water-insoluble polymer in which at least 90% of the particles capable of sticking have a size of less than 0.3 microns.  22. Dispersion according to claims 16 19, characterized in that it contains capable of sticking polymer particles obtained from monomers selected from the group: styrene, vinyl acetate, ethylene, ethyl vinyl ether, butyl vinyl ether.  23. Dispersion according to claims 16 to 19, characterized in that the water-soluble polymer is selected from the group consisting of starch, liquefied starch simple hydroxyethyl ether, polyvinyl alcohol, hydroxypropyl methylcellulose, polysaccharide resins, polyethylene glycol, maltodextrin and a starch hydrolysis product with an intrinsic viscosity of at least 0.12 for  24. Dispersion according to claims 16 to 19, characterized in that it contains at least 30% solids by weight of the dispersion.  25. The dispersion according to item 16 19, characterized in that it contains 60% of solid particles by weight of the dispersion.  26. The dispersion according to claim 16 or 19, characterized in that it contains styrene-butadiene rubber as a water-insoluble component.  27. Dispersion according to paragraphs. 16 19, characterized in that as a water-insoluble component contains a simple hydroxyethyl ether of liquefied starch.  28. Dispersion according to paragraphs. 16 to 19, characterized in that as a water-soluble component contains polyvinyl alcohol.  29. Dispersion according to paragraphs. 16 to 19, characterized in that it contains a water-soluble component mixed with a water-soluble polymer, which is able to inhibit the adhesion of polymer particles. 30. A polymer composition in the form of a dried powder, comprising a water-insoluble polymer based on vinyl and diene monomers having a glass transition temperature below 55 ^o C, and a water-soluble component, characterized in that the water-insoluble polymer is a particle of which at least 90% have a particle size of less than 1 μm, as a water-soluble component, it contains either a water-soluble polymer capable of inhibiting the adhesion of particles of a water-insoluble polymer, or a mixture of a water-soluble polymer with a substance, having the indicated property, contained in an amount of 5 to 10% by weight of a water-soluble polymer, and the weight ratio of the water-insoluble polymer to the water-soluble component is (3 75) (25 97).  31. The composition according to p. 30, characterized in that it contains a water-soluble component, which includes 50 to 80 wt. solids.  32. The composition according to p. 30, characterized in that it contains a water-insoluble polymer in which at least 90% of the particles have sizes less than 0.5 microns.  33. The composition according to p. 31, characterized in that it contains a water-insoluble polymer in which at least 90% of the particles have sizes below 0.3 microns.  34. The composition according to p. 30, characterized in that as capable of sticking polymer particles contains polymers obtained from monomers selected from the group: styrene, 1,3-butadiene, vinyl acetate, ethylene, ethyl ether.  35. The composition according to p. 30, wherein the water-soluble polymer is selected from the group comprising starch, liquefied starch simple hydroxyethyl ether, polyvinyl alcohol, hydroxypropyl methylcellulose, polysaccharide resins, polyethylene glycol and maltodextrin.  36. The composition according to p. 30, characterized in that it contains a water-soluble component, including the starch hydrolysis product, with an intrinsic viscosity of less than 0.12 dl / g.  37. The composition according to p. 30, characterized in that it contains a styrene-butadiene copolymer as a water-insoluble component.  38. The composition according to p. 37, characterized in that as a water-soluble component it contains polyvinyl alcohol.  39. The composition according to p. 30, characterized in that it contains a liquefied gelatinized starch and a reaction product of a liquefied gelatinized starch and one or more unsaturated monomers containing 10 to 70 wt. diene, with a mass ratio of unsaturated monomers and starch from 2 10 to 30 10.  40. The composition according to p. 39, characterized in that it contains a reaction product initiated by persulfate ions.  41. The composition according to p. 40, characterized in that it contains a reaction product in which the diene is 1,3-butadiene, and the second unsaturated monomer is styrene at a mass ratio of unsaturated monomers and starch from 2 10 to 23 10.  42. The composition according to p. 30, characterized in that it contains a water-soluble component in a mixture with a water-soluble polymer, which is able to inhibit the adhesion of polymer particles. 43. A method of obtaining a polymer composition in the form of a dry film, comprising the preparation of a stable aqueous polymer dispersion containing a water-insoluble polymer based on vinyl and diene monomers having a glass transition temperature below 55 ^° C, a water-soluble component and water, and then forming a film, characterized in that a water-insoluble polymer is used in the form of particles, at least 90% of which have a size of less than 1 μm, or a water-soluble polymer capable of inhibiting is used as a water-soluble component the stickiness of the particles of a water-insoluble polymer, or a water-soluble polymer and a substance having the indicated property, contained in an amount of 5 to 10% by weight of the water-soluble polymer at a weight ratio of the water-insoluble polymer to the water-soluble component (3 75) (25 97) and the total solids content of the suspension 20 60 wt. . and the film is formed by applying a dispersion to a solid surface, followed by drying.  44. The method according to p. 43, characterized in that as a component not dissolved in water, a dispersion is used that contains a copolymer obtained from monomers selected from the group of ethylene, vinyl acetate, 1,3-butadiene and styrene.  45. The method according to p. 44, characterized in that the dispersion which contains a styrene-butadiene copolymer is used as a water-insoluble component. 46. A method of obtaining a polymer composition in the form of a dried powder, comprising the following operations: preparation of a stable aqueous polymer dispersion containing a water-insoluble polymer based on vinyl and diene monomers, including capable of sticking polymer particles having a glass transition temperature below 55 ^o C, a water-soluble component and water, followed by obtaining a powder from the dried dispersion, characterized in that the water-insoluble polymer is used in the form of particles, of which at least 90% have a particle size of ry less than 1 micron, and as the water soluble component used contains a water soluble polymer capable of inhibiting coalescence of the polymer particles, or, a mixture of a water-soluble polymer and a component capable of inhibiting coalescence of the polymer particles, wherein the coalescable particles of a water-insoluble polymer is 3 75 wt. solids, and the water-soluble component contains 25 97 wt. solids, with 5 to 10 wt. from these 25 97 wt. may constitute a component capable of inhibiting the adhesion of a dry dispersion.  47. The method according to p. 46, wherein the aqueous dispersion is dried or sprayed, or on a drum, or vacuum.  48. The method according to p. 46, characterized in that it includes the operation of selective deposition of particles in a solvent.  49. The method according to p. 46, characterized in that the dispersion is obtained by the interaction of liquefied gelatinized starch with one or more unsaturated monomers (monomer) containing 10 to 70 wt. diene, with a mass ratio of monomer and starch from 2 10 to 30 10.  50. The method according to p. 49, characterized in that the reaction of starch and monomer is carried out in the presence of catalytic persulfate ions.  51. The method according to PP. 49 and 50, characterized in that as the monomer use diene, which is 1,3-butadiene, and the second unsaturated monomer is styrene, while the mass ratio of the unsaturated monomer and starch is from 2 10 to 30 10.  52. The method according to p. 49, characterized in that the use of a water-soluble component in a mixture with a water-soluble polymer capable of inhibiting particle adhesion.  55. The dried powder obtained from the polymer composition by the method according to p. 46. 54. A method of obtaining a stable aqueous polymer dispersion, comprising preparing a dried water-dispersible film or powder based on a mixture of a water-insoluble polymer from vinyl and diene monomers having a glass transition temperature below 55 ^° C and a water-soluble component, mixing the dried film or powder with water with obtaining a dispersion containing 20 to 60 wt. solids, characterized in that a component insoluble in water is introduced into the mixture, which includes polymer particles capable of sticking together, obtained from diene and vinyl monomers having a glass transition temperature below 55 ^° C and at least 90% of which have dimensions less than 1 μm and as a water-soluble component use a water-soluble polymer capable of inhibiting the adhesion of polymer particles, or use a mixture of a water-soluble polymer with a component capable of inhibiting the adhesion of polymer particles, and obnye coalescable water insoluble particles is 3 to 75% by weight of solids, however, the water soluble component is 25 97% by weight of solids, of which 5 10 wt. these 25 97 wt. may constitute a component capable of inhibiting adhesion.  55. The method of claim 54, wherein a water-soluble component is used that contains a water-soluble polymer capable of inhibiting the adhesion of polymer particles. 56. A method of obtaining a stable aqueous polymer film-forming dispersion, comprising mixing a water-insoluble polymer based on vinyl and diene monomers having a glass transition temperature below 55 ^o C, a water-soluble component and water, characterized in that the water-insoluble polymer is used in the form of particles, at least 90% of which have a size of less than 1 μm, either a water-soluble polymer capable of inhibiting the adhesion of particles of a water-insoluble polymer or a water-soluble one is used as a water-soluble component a polymer and a substance having this property, contained in an amount of 5 to 10% by weight of a water-soluble polymer, mixing is carried out at a weight ratio of a water-insoluble polymer, a water-soluble component (3 75) (25 97) and a dry substance water (20 60) (40 80).  57. The method according to p. 56, characterized in that it includes the operation of mixing an aqueous dispersion of a water-soluble component and an aqueous dispersion of particles of a water-insoluble polymer.  58. The method according to p. 56, characterized in that the dispersion is obtained, which contains 60 wt. solids.  59. The method according to p. 56, characterized in that a mixture of a water-soluble component and a water-soluble polymer capable of inhibiting the adhesion of polymer particles is used.  60. A film-forming composition for treating paper and paper products, comprising a pigment and a binder, an aqueous polymer dispersion, characterized in that it contains a film-forming dispersion according to claim 16, as a binder, wherein the binder pigment mass ratio is 100 18 and the dry matter content in the composition equal to 59 66 wt.  61. The method of applying a film coating to paper, comprising applying a film-forming composition to paper at room temperature and then drying it in a dryer, characterized in that the composition for processing paper according to claim 60 is used as the film-forming composition.  62. Paper material with a film coating, which is a sheet of paper connected to a polymer film, characterized in that as the polymer film includes a composition according to claim 1.  63. Paper material with a film coating, which is a sheet of paper connected to a polymer film, characterized in that the polymer film includes a film-forming composition according to claim 60. Priority on points:
02/05/91 for PP. 1 5, 7 20, 22 32 and 34 46;
12.19.91 PP 6, 21, 33, 47 and 48.

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